Protective coating compositions from aliphatic condensed polyunsaturated fatty alcohols and their esters



United States Patent ()fi Patented Sept. 13, 1960 ice PROTECTIVE COATING COMPOSITIONS FROM ALIPHATIC CONDENSED POLYUNSATURATED FATTY ALCOHOLS AND THEIR ESTERS Lyle E. Gast, John C. Cowan, and Howard M. Teeter, Peoria, Ill., assignors to the United States of America as represented by the Secretary of Agriculture No Drawing. Filed July 31, 1958, Ser. No. 752,385 3 Claims. (Cl. 106-287) (Granted under Title 35, US. Code (1952), see. 266) This invention relates to protective coating compositions prepared by the condensation of polyunsaturated fatty alcohols in the presence of an alkaline catalyst and boron compounds. The polyunsaturated alcohols used in the preparation of these coating compositions were mixtures or oleyl, linoleyl and linolenyl alcohols derived from drying and semi-drying oils such as linseed, soybean and safilower oils.

Esters of the condensed polyunsaturated alcohols are prepared by reacting the condensed alcohols with monoand dicarboxylic acids, particularly acrylic acid, sorbic acid, maleic acid and soybean oil fatty acids, in the presence of an acid catalyst.

More specifically, the condensed alcohols and their esters prepared by the above reactions are obtained by heating polyunsaturated fatty alcohols derived from drying and semi-drying oils containing oleic, linoleic, linolenic or other unsaturated fatty alcohols in the presence of an alkaline catalyst and a boron compound. The produced condensed alcohols are yellow oils insoluble in water but soluble in organic solvents. They are further characterized by molecular weights of 600 to 800, iodine values of 80 to 95, hydroxyl content of 2.5 to 3.5 percent, low free fatty acid content and absence of carbonyl groups.

These condensed alcohols and esters have the unexpected property that they can be baked under suitable conditions to form hard tack-free films which show good resistance to acids, alkalis, detergents, solvents and water.

The following examples illustrate the preparation of the unsaturated condensed alcohols:

EXAMPLE 1 A mixture of 268 g. (1 mole) soybean alcohols, potassium hydroxide (0.30 mole) and boric anhydn'de (0.15 mole) was placed in a 1000 ml. round bottom flask fitted with a stirrer, thermometer, nitrogen inlet tube and a large diameter outlet tube. The contents were heated rapidly with stirring to 300 C. Evolution of water occurred at 120-150 C. and was removed immediately from the reactor by distillation through the outlet tube. A rapid evolution of gas occurred at 170 C. After this no other products were evolved except an occasional small quantity of water. The reaction mixture was held at 290-310 C. for 26 hours during which time the color varied from brown at the beginning to light yellow heating time are as follows:

at the end of the heating period. Some soybean alcohol distilled through the outlet tube during the heating period. The product was dissolved in benzene, washed free of alkali and dried by removal of the solvent under vacuum. The resulting condensed aliphatic fatty unsaturated alcohols amounted to approximately 200-230 g. Analytical data on the product React. I.V. Hydroxyl, 1 Acid Carbonyl Vise. Mol. Time Percent No. 02 (Gardner) Wt.

EXAMPLE 2 Under conditions generally similar to those cited in Example 1, 266 g. (1 mole) of linseed alcohols, potassium hydroxide (0.3 mole) and boric anhydride (0.15 mole) were heated at 300 C. for 3 hours. This proced-ure gave 220 g. of condensed aliphatic polyunsaturated alcohols. I.V., 92; hydroxyl, 3.14 percent; mol. wt., 675; Gardner viscosity Y.

EXAMPLE 3 The esters of the condensed aliphatic polyunsaturated alcohols were prepared as follows:

Several esters of condensed aliphatic polyunsaturated alcohols derived from soybean and linseed oils were prepared by refluxing stoichiometric amounts of the appropriate alcoholic product and acid with p-toluene sulfonic acid 1% by weight of the charge) in toluene. After 3 hours refluxing, the resulting esters were washed with water, sodium carbonate and finally with water until washings tested neutral. The acid values of the condensed aliphatic polyunsaturated alcohol esters were as follows:

Condensed Polyunsaturated Alcohol Ester Soybean Linseed Acrylic 6. 3 1. 2 Sorbic 4. 8 2. 0 Maleic 13. 0 l3. 3 Soybean 10. 7 1.1

Films of condensed aliphatic polyunsaturated alcohols derived from soybean and linseed oils and their sorbic, acrylic, maleic and soybean esters were prepared by dissolving 1 g. of the condensed aliphatic polyunsaturated alcohol or ester in 3 grams of toluene containing cobalt naphthenate drier. These compositions can be baked for 1 hr. at 150 C. or for 20 min. at 200 C. to form hard tack-free films. Hardness and solvent resistance of these films are shown in Tables I and II. The films baked at 150 C. were harder than those baked at 200 C. Films show good resistance to 18 percent hydrochloric acid, 5 percent sodium hydroxide, 2 percent alkaline sulfonated hydrocarbon, percent ethanol, white gasoline, ethyl acetate, acetone, benzene, and water. chloroform produces frosting or swelling of some films within one hour.

obtained from 2-6 hours" 3 4 Table I lar Weight of 600 to 800, an iodine value of 80 to 95, and FILM-PROPERTIES OF BAKED CONDENSED POLYUN- a hydroxyl content of t P reacting the SATURATED FATTY ALCOHOLS CON AI IN C B L condensed alcohol with an organic acid selected from DRIER the group consisting of acrylic acid, sorbic acid, maleic 5 acid, and soybean oil fatty acids to form an ester, and cgndensed dissolving said ester in a solvent containing a cobalt napthenate drier to form a coating composition.

Test Reagent soybean Linseed 2. A process comprising heating an alcohol selected 7 o from the group consisting of oleyl alcohol, linoleyl alco- 200 (lb hol, linolenyl alcohol, and mixtures thereof, in the pres- Hardness 3 a 3 2 V ence of an alkaline catalyst and a boron compound to 18% 1: M55531: I-'51:: fig'if 'j'jj hrs), form a condensed alcoholhaving an average molecular 5% NaoHm {135 1 3 d 5( i F hm). weight of 600 to 800, an iodine value of 80 to 95, and

m n a hydroxyl content of 2.5 to 3.5 percent, and dissolving wht a El i said condensed alcohol in a solvent containing a cobalt entitie w 1155.11: K811551531: I nopthonate dn'or to f a coating compositiongg 3. A process of forming a hard, tack free film, WhlCh ghlorofdfnil 1 5 151153: aging: g is resistant to aciglsiflalkaliesi detergents, solvents and waenzene. r 4 r5 f ter, comprising a mg a fi 111 formed from a base dis- Water hrs) hrs) solved 1n a solvent containing a cobalt naphthenate l Baked for 1 hr drier, said base being selected from a condensed alcohol b Baked lilor g0 t produced by heating an alcohol selected from the group .ggg g i Pi g: attaekmfi hm consisting of oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and mixtures thereof, in the presence of an al- Table H 25 kaline catalyst and a boron compound to form a con- ALKALI RESISTANCE AND HARDNESS OF' FILMS 5 3 mg; densed alcohol having an average molecular Weight of ggggggfiggg gggq g ggrgggsgj A 0 O 600 to 800, an iodine value of so to 95, and a hydroxyl content of 2.5 to 3.5 percent, and an ester produced by Compound Hardness 5 Percent reacting said condensed alcohol with an acid selected from NaOH the group conslstmg of acrylic acid, sorbic acid, maleic acid, and soybean oil fatty acids.

Condensed aliphatic pol%unsat11irated al- 3 D(15 min) 2 81 11 31 1 15 References Cited in the file of this patent oi fi iffi egii 2 0 1 11 35 UNITED STATES PATENTS oglhigzd liifiiai polyunsaturated a1 a D(8 hrs J 2, Barrett et a1 Sept. 13, 1938 Soobiioldtorivodirom Linseed 01 2 S; hrs) 2,137,616 Hann Nov 22, 1938 ii iic isf gi 3 2 11159. 2,1 6,671 Ellis Feb. 7, 1939 0y can es er rs. 2,7 3 780 Koenecke 6t 11. Dec. 11 1956 rs) 2,836,628 Miller May 27, 1958 g fi zi fi 2,861,110 Herzenberg et al. Nov. 18, 1958 We claim: 79,965 Germany July 29, 1929 1. A process comprising heating an alcohol selected 164,026 Austria Sept, 26, 1949 from the group consisting of oleyl alcohol, linoleyl alcohol, linolenyl alcohol, and mixtures thereof, in the OTHER REFERENCES presence of an alkaline catalyst and a boron compound Sulzbacher: J. Appl. Chem, December 5, 1955, pp. to form a condensed alcohol having an average molecu- 637-641.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent Noo 2,952,556 September 13, 1960 Lyle Ea Gast et a1;

It is herebjr certified that error appears in the-printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 2, line 15, in the table, third c0 1u1mn thereof, under the heading, "Hydroxyl, Percent", last line, for "3.60" read 2.60

Signed and sealed this 11th day of April 1961..

(SEAL) Attest:

iW; SW'DER ARTHUR W. CROCKER Attesting Oflicer Acting Commissioner of Patents 

1. A PROCESS COMPRISING HEATING AN ALCOHOL SELECTED FROM THE GROUP CONSISTING OF OLEYL ALCOHOL, LINOLEYL ALCOHOL, LINOLENYL ALCOHOL, AND MIXTURES THEREOF, IN THE PRESENCE OF AN ALKALINE CATALYST AND A BORON COMPOUND TO FORM A CONDENSED ALCOHOL HAVING AN AVERAGE MOLEULAR WEIGHT OF 600 TO 800, AN IODINE VALUE OF 80 TO 95, AND A HYDROXYL CONTENT OF 2.5 TO 3.5 PERCENT, REACTING THE CONDENSED ALCOHOL WITH AN ORGANIC ACID SELECTED FROM THE GROUP CONSISTING OF ACRYLIC ACID, SORBIC ACID, MALEIC ACID, AND SOYBEAN OIL FATTY ACIDS TO FORM AN ESTER, AND DISSOLVING SAID ESTER IN A SOLVENT CONTAINING A COBALT NAPTHENATE DRIER TO FORM A COATING COMPOSITION. 